CN85101472A - Combined ceramic products and production method thereof - Google Patents
Combined ceramic products and production method thereof Download PDFInfo
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- CN85101472A CN85101472A CN85101472.0A CN85101472A CN85101472A CN 85101472 A CN85101472 A CN 85101472A CN 85101472 A CN85101472 A CN 85101472A CN 85101472 A CN85101472 A CN 85101472A
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Abstract
On ceramic component, form one deck carbon film, or on this carbon film, form layer of metal film, thereby then this ceramic component is formed a composite product with ceramic component or hardware in addition are bonding.This composite product has high cohesive strength and can rupture in the bonding part hardly.
Description
The present invention relates to a kind of new ceramics composite product and production method thereof.
Combined ceramic products of the present invention is applicable to the turbo-supercharger of automobile, the electrode of store battery, suchlike devices such as the composition material of gas sensor.
In recent years, the field of ceramic applications is expanded greatly, and it is applied in many different fields and goes now.But pottery uses seldom individually, is to combine with the form of matrix material with other materials to use habitually in the past.And the use of this form has further enlarged its Application Areas.If pottery can easily constitute matrix material with other materials, so just can produce many new functions and new characteristic.
Some methods that a pottery is lumped together with another part ceramic junction commonly used all have been known, as:
(1) disclosed method among the Japanese Patent prospectus NO.84185/83, this method are silicon carbide powder to be packed in treat between the agglutinating ceramic surface, carry out equipressure then and handle in the scope of 1600 ° to 2000 ℃ of temperature.In this method, because the use heat isopiestic method, so sticking temperature wants high and want the shape and size of agglutinating material all to be restricted.
(2) disclosed method among the Japanese Patent prospectus NO.75976/80, this method are to use CuS, LaCrO
3And SiO
2Add a kind of organic solvent and the lotion for preparing is coated between the pottery in powder, then heating lotion and make it to react between 1000 ° to 1200 ℃ of temperature.This method is owing to the blending ratio of powder will become with the kind of pottery, so poor reliability.
(3) disclosed method among the Japanese Patent prospectus NO.88184/83,93402/74,130865/80 and 79876/83, this method are by containing the pottery of silicon nitride treating between the agglutinating ceramic surface that filling layer of metal oxide compound or metal nitride or metallic carbide bond.Because metal is directly to be bonded on the pottery, so none can bond together metal layer with pottery securely in the aforesaid method.
On the other hand, commonly used also is known with metal with ceramic bonding method together, and these methods generally are that (W, W-MO MO-Mn), use method for welding then and make and metalized coatedly connect with metal at the ceramic surface spraymetal.
Japanese Patent prospectus NO.113683/80 and NO.96784/81 are to how the spraymetal layer is described.But, all these methods all be directly metal bonding to pottery, this just makes metal plating itself to bond securely with this pottery.
The purpose of this invention is to provide and a kind ofly form, have a manufacture method of composite product and these goods of high bond strength by the ceramic component that bonds together.
Another object of the present invention provides a kind ofly to be made up of the same hardware of a ceramic component, has a manufacture method of product and this product of high bond strength.
(I) does an explanation to composite product and the manufacture method thereof be made up of ceramic component now.
Main points of the present invention are a kind of Ceramic Composite goods, it is characterized in that ceramic component is that diffusion by carbon bonds together.
Say that with regard to ceramic component the material with any composition can use, and the ceramic component of the ceramic component of same material or non-same material also can bond together.Can from following respectively organize to select at least the material a kind ofly use as stupalith: oxide compound, nitride, carbide, silicide, boride and graphite.
Oxide compound includes oxide compound such as the Al that mainly is made of a kind of component
2O
3, BeO, ZrO
2, CaO, SiO
2, MgO, ThO
2, TiO
2And mullite (Al
2O
3-SiO
2).
Nitride includes nitride such as the Si that mainly is made of a kind of component
3N
4, AlN, BN, Be
3N
2, ZrN, NbN, VN and TiN.
Carbide includes carbide such as SiC, the B that mainly is made of a kind of component
4C, TiC, WC, TaC, NbC, HfC, ZrC and VC.
Silicide includes TiSi
2, ZrSi
2, HfSi
2, VSi
2, NbSi
2, TaSi
2, CrSi
2, MOSi
2, WSi
2, or the like.Boride includes TiB
2, ZrB
2, HfB
2, VB
2, NbB
2, TaB
2, CrB
2, MOB
2, WB
2Or the like.
In the present invention, dose treating the carbon part ground between the bonding surface or spread fully and be penetrated in the stupalith and go, thereby make two kinds of materials bond together securely.With regard to combined ceramic products of the present invention, two kinds of bonding situations are arranged: a kind ofly be, filling one deck carbon film makes its diffusion then and infilters in two ceramic components and goes between the surface of ceramic component, diffusion by carbon film and carbon film itself and stupalith is bonded together; Another kind is, whole carbon film all is penetrated in the ceramic component and goes, and ceramic component directly bonds together then.Be packed in ceramic component and treat that the carbon film between the maxxaedium is very firm and has very high strength, and 10 Ω preferably of the specific resistance during its room temperature, cm or littler.
Clog in ceramic component and treat that the carbon film between the bonding surface is that this organic method of heating obtains in non-oxidizing atmosphere then by a kind of special organic substance of coating on the ceramic component surface.In addition, it also can obtain by at high temperature decomposing a kind of organic gas and making degradation production be deposited on the lip-deep method of ceramic component.Preferably 10 microns or less than 10 microns of carbon film thickness are if thickness is 3 microns or then better less than 3 microns.The carbon film minimum thickness is advisable with 0.1 micron.
According to the state of the carbon that thermolysis produced, organic substance can be divided into following (a) generally to (d) four classes.Use wherein (c) class and (d) organic substance of class just can form the strong carbon film of strong yet cohesive force of the present invention.Therefore preferably by (c) class and (d) the formed carbon film of organic substance in the class pottery and ceramic phase are bondd or make ceramic and metallic alloy bonding.
Use the organic substance in (d) class then better.When using (C) class and (d) during the organic substance in the class, the room temperature tensile strength of the carbon film of carbonization is preferably 10 kilograms/millimeter
2Or higher, if reach 20 kilograms/millimeter
2Or it is higher then better.
No matter adopt which type of organic substance, the room temperature Vickers hardness of carbon film of the present invention preferably 100 or higher is if room temperature Vickers hardness reaches 300 or higher then better.
(a) when thermolysis or when gasification, whole organic compound is sent forth, does not therefore have the vitrification carbon film to form at ceramic surface at all.Organic solvents such as ethanol, acetone, trieline just belong to this class.
(b) small part forms the vitrification carbon film, and major part then forms the carbon film carbon black type or the coke type.Resin as ethyl cellulose, polyethylene, polystyrene, polypropylene, Vaseline, polyacrylamide, aldehyde resin, polysulfones and polybutene hydrochlorate etc. and so on just belongs to this class.These organic substances can not produce the carbon film of cohesive force.
(C) most of carbon film that forms vitrification carbon type, and only small part forms the carbon film of carbon black type or coke type.This carbon film has certain cohesive force, therefore stupalith can be bonded together with metallic alloy with stupalith or with stupalith.For example, resol, polyimide resin, aldehyde resin, polycarbonate, polysulfone resin, poly-fluorine second diene resin etc. just belong to this class.
(d) with hard, glossiness and carbon film form vitrification remains at ceramic surface for the part carbon in the organic compound or whole carbon, and this carbon film is boning securely with ceramic surface.For example, as the thermosetting resin of Resins, epoxy, alkyd resin, poly-third butylene resin etc. and so on, and the thermoplastic resin that resembles polyvinyl chloride (PVC) RESINS, vinyl-acetic resin etc. and so on just belongs to this class.These resins of general requirement do not contain the material that produces thing beyond the carbon film when those heat resin and it is decomposed in rare gas element as far as possible.According to this viewpoint, in the above-mentioned resin of mentioning, preferably adopt Resins, epoxy and the poly-third butylene resin.In addition, ad hoc proposal adopts bisphenol A epoxide resin in Resins, epoxy.
The preferably highly purified rare gas element of atmosphere during heating, for example argon gas or helium.If in inert atmosphere residual any can be with the material of carbon react with, oxygen for example, so a part of carbon will become carbon ash or cinder, so just can not form high cohesive force of the present invention, firm carbon film.
In inert atmosphere, can adopt any pattern thermal source.For example, electric furnace is exactly the simplest a kind of equipment, and thermals source such as infrared rays, laser beam, electron beam also can adopt.
In addition, also can use plasma chemistry vapor deposition (CVD) and finish task of the present invention.
Can also be by the method for heating ceramic and organic substance rather than by organic substance being coated to the method for ceramic surface respectively in identical atmosphere, the carbonaceous gas that is produced by organic substance forms one deck carbon film on ceramic surface.This method can also be used for producing new composite ceramics, and carbon film is securely with the institute's agglutinating ceramic surface that requires bonding in this composite ceramics.
On the other hand, composite ceramics with strong cohesive force interface can also easily obtain by following method, be about to that specific organic substance is coated on the ceramic surface to be glued or two treat that sticking ceramic surface all is coated with and apply this organic substance, by the organic solvent effect two potteries are pasted together mutually, the heating organic substance makes its decomposition in non-oxidizing atmosphere then.
The organic compound that is adopted in this case, suggestion adopt above-mentioned (c) class and (d) organic substance in the class, and Resins, epoxy, poly-third butylene resin and the alkyd resin are adopted in special recommendation.Adopt these organic substances just can obtain above-mentioned the sort of high-adhesion, firm carbon film.In addition, even adopt the organic substance of the carbon that can form carbon ash shape in (b) class like that,, then still can obtain firm bond effect if stupalith is directly bonded together by diffusion energy.
Although cohesive action of the present invention can carry out need not to apply a pressure by dead weight, apply a pressure and can obtain firm bonding.Preferably 20 kilograms/millimeter of institute's applied pressures
2Or more a little bit smaller, pressure is 3～15 kilograms/millimeter
2Then better.
Almost the temperature of carbonization is to stupalith softening temperature or low slightly from organic substance for the Heating temperature scope in the bonding process, and comparatively the ideal temperature range is 800 ℃ to 2000 ℃, and temperature range is then better to 1500 ℃ from 1000 °.The organic substance carbonization is finished in about 800 ° to 1500 ℃ scopes, is higher than 1500 ℃ of then greying phenomenon appearance, and the carbon film that is obtained in these temperature ranges has very high intensity and cohesive force like that just as top the narration.
(II) is existing just by ceramic component being obtained ceramic composite with metal bonding and manufacture method is done an explanation.
Second invention of the application is ceramic composite, it is characterized in that stupalith is by treat to form the firm carbon film of one deck on the bonding surface at stupalith with the bonding of metal.Employed stupalith can be an identical type, also can be different types of.Carbon film is high-adhesion as mentioned above like that, and carbon film firm, vitrification is then better.This carbon film is to form under the condition of going in carbon is diffused into pottery as base material, therefore has high cohesive force.Preferably a kind of solder of employed metal in this carbon film mull technique.Carbon film of the present invention is goodish with the wetting capacity of spelter and solder.
Suitable solder includes silver solder, copper solder, nickel solder, brazing spelter, crooked chisel material etc.Silver solder includes: by 40%～60%(weight) silver, 20%～35%(weight) copper and 15%～30%(weight) the alloy formed of zinc; Add 15%～25%(weight by above-mentioned each component) the alloy formed of cadmium; By 70%～75%(weight) silver and 25%～40%(weight) the alloy formed of copper; By 80%～90%(weight) silver and 10%～20%(weight) the alloy formed of manganese or the like.The copper solder includes fine copper; Contain 60%(weight) or lack the brass alloys of the zinc of some slightly; By 4%～10%(weight) phosphorus, 4%～7% or 10%～20%(weight) silver, the alloy that all the other are formed for copper; By 35%～40%(weight) gold, the alloy that all the other are formed for copper; Contain mauganin or the like.The nickel solder includes and contains 15%～25%(weight) nickelalloy of manganese; Contain 10%～20%(weight) chromium, 2%～5%(weight) boron and total amount be 10%(weight) or lack the nickelalloy or the like of some iron, silicon and carbon slightly.Contain a kind of element words that can form carbide in the solder material, then this braze material is big especially with the wetting capacity of solder, thereby can access firm bonding.When carbon film was still kept intact in the bonding part, then this film peeled off easily in use, so do not allow carbon film freely not have bundle when boning.
The Ceramic Composite goods recommended the most of the present invention obtain the metallic membrane of such formation with metal bonding then by forming a metallic membrane (each carbon film is again to treat to form on the agglutinating ceramic surface) on the firm carbon film together in addition.The metallic membrane of Xing Chenging can further improve the wetting ability with spelter and solder like this.The silver solder of mentioning above can adopting in this case, brazing spelter, nickel solders etc. are as braze material.Employing is such as a kind of metal powder cream of coating, and vacuum evaporation sprays, and the method for plating or the like can form metallic film.Also can adopt tinsel.In addition, form after the metallic membrane, be preferably in to heat in the non-oxidizing atmosphere metallic membrane is worked with carbon film by a kind of like this method.
For the metallic membrane that makes shape on the carbon film that forms on the ceramic surface coexists ceramic surface firmly links to each other, can react and the metal or alloy that forms carbide is used as forming the material of metallic membrane with carbon film when preferably adopting those to be heated to sticking temperature.Preferably adopt chromium, nickel, manganese, iron, vanadium, titanium, nickel solder, cupromanganese solder, crooked chisel material or the like.
(III) is now bonding with hardware with regard to ceramic component and Ceramic Composite goods and manufacture method thereof that obtain are done an explanation.
The 3rd invention among the present invention mainly is a kind ofly to be bonded together with hardware and the Ceramic Composite goods formed by ceramic component, it is characterized in that the above-mentioned pottery of mentioning is bonding with hardware by formed firm carbon film on ceramic surface with a kind of metal.The formation of firm carbon film and the kind of braze material are identical with top situation in said.
In addition, this invention is a kind of Ceramic Composite goods still, it include one the formed metallic membrane of the carbon film on the aforementioned ceramic component and one with the hardware of metal bonding to the metallic membrane.Said the same in the method that on carbon film, forms metallic membrane and (II).Form after the metallic membrane it in inert atmosphere or be heated to 500 ℃ or higher in a vacuum but generally be preferably in, form the layer of metal coating by such method, preferably adopt chromium, manganese, nickel, iron or contain the material of the alloy of these elements as the acquisition metallic membrane.
(IV) another invention is a kind of Ceramic Composite goods, it is characterized in that having on ceramic material surfaces a firm carbon film.Carbon film a kind of carbon film of vitrification preferably according to the present invention.The frictional coefficient of this carbon film cans be compared to most the big of stupalith, and (Vickers' hardness: HV100) rub that this carbon film also can not peel off and almost not damage, the material that is formed with this carbon film is suitable as the material that sliding part is used both to have used ferrous metal.
(V) another invention is a kind of Ceramic Composite goods, it is characterized in that it has the firm carbon film that one deck contains metallic particles or ceramic particle on the surface of stupalith.So owing to be formed with coarse that metallic particles or ceramic particle ceramic material surfaces can do, this with regard to make be right after and come obtain firm bonding with soldering and become possibility.
Preferably adopt the above-mentioned metal or alloy that can form carbide to be used as metallic particles, can adopt above-mentioned various pottery to be used as ceramic particle.
(VI) another invention is a kind of Ceramic Composite goods, it is characterized in that being formed with on the whole surface of stupalith the firm carbon film of one deck.It utilizes carbon film to be used as the protective membrane of this stupalith.In ceramic, some graphite product is softer, peels off into fragment easily, and such graphite product just can be protected by forming the firm carbon film of one deck on its whole surface.
The present invention's formed all carbon films in ceramic composite illustrated in above-mentioned (I) to (VI) can be got rid of by being heated to the pyritous method in air.Therefore also be nothing the matter separately again the material that bonds together.An embodiment of ceramic composite of the present invention is exactly the turbo-supercharger that automobile is used, turbo-supercharger preferably has following array structure in this case: it has a pair of blade that is installed in axle two ends, blade be pottery and another blade is a metal, two blade pass are crossed axle and are connected, and metal blade is by treating that at ceramic blade formed carbon film is bonding with ceramic blade with metal on the agglutinating surface.In this turbo-supercharger, preferably adopt silicon nitride and silicon carbide sintered part to be used as ceramic blade.Preferably adopt carbon steel to make metal blade.In order to make ceramic same metal bonding, preferably adopt the Cu-Mn alloy, Ni-Cr alloy or Ni-Mn alloy.
In addition, matrix material of the present invention can be used for the electrode as store battery, and aluminum oxide is suitable for as stupalith in this case, and stainless steel is suitable for using as metal.In order to bond with a kind of metallographic phase, the braze material of mentioning above preferably adopting.
Now accompanying drawing is made a brief description.
Fig. 1 is the graph of a relation between the Heating temperature of decomposing organic matter matter and the carbon resister coefficient that obtained.
Fig. 2 is the graph of a relation between stupalith sticking temperature and the transverse strength.
Fig. 3 is the auger analysis figure as a result of formed carbon film on Ceramic Composite product surface of the present invention.
Fig. 4 is the turbo-supercharger skeleton view that is used for automobile of the present invention.
Embodiment 1
Fig. 1 is the graph of a relation between the specific resistance of the carbon film that forms on Heating temperature and the ceramic surface.The bisphenol-type epoxy resin that can buy on the market is coated to the Si of sintering consolidation
3N
4On the ceramic surface (epoxy equivalent (weight) of this Resins, epoxy is 183～193, and its molecular weight is 330, and trade name is EPiKOte815), in argon atmospher, heat this Resins, epoxy (flow velocity of argon gas is 8 liters/minute) then.In this case, when being heated to 350 °～400 ℃ (rate of heating is 100 ℃/minute) and be incubated 3 minutes under this temperature, this Resins, epoxy is at first emitted gas.(rate of heating is 200 ℃/insulation 3 minutes min) and under this temperature, allows its naturally cooling then then Resins, epoxy to be heated to a predetermined temperature.As shown in Figure 1, when Resins, epoxy is heated to 800 ℃ or higher, specific resistance descends rapidly, so formed a conduction, the carbon film of vitrification.The specific resistance of this layer carbon film improves and the reduction and the specific resistance of kish in the time of about 1500 ℃ that level off to along with Heating temperature.
The thickness of this layer carbon film is approximately 1 micron through measurement.Carbon film thickness can change arbitrarily by the method for coating Resins, epoxy on ceramic surface.Temperature is lower than 700 ℃, and this Resins, epoxy maintains the original state, and carbonization is expansion not, so specific resistance increases.Therefore, be necessary Resins, epoxy is heated to 700 ℃ or highlyer make its carbonization and go so that carbon is penetrated in the ceramic post sintering spare.
When being heated to 800 °～1500 ℃ in inert atmosphere, the carbon film that is obtained mainly is made up of the crystallization graphite that amorphous vitrification carbon is added small part.Find that by various analytical resultss Heating temperature is 1500 ℃ or higher, quantity of graphite also increases except that amorphous carbon.This point also is confirmed by specific resistance curve among Fig. 1.
As mentioned above, no matter still can arbitrarily form by changing Heating temperature with the carbon film of kish for its main ingredient with the carbon film of amorphous carbon for its main ingredient.
The carbon film that forms on ceramic surface with aforesaid method is by also bonding together with ceramic surface securely that chemical reaction generates, therefore carbon film can not be disposed from ceramic surface except adopting such as the method additive method of throwing this machinery.
At the formed carbon film of ceramic surface is adamantine, when room temperature, even also can not scratch it fully with the stainless steel needle with Vickers' hardness 150.
Clearly, the carbon film of this example is heated to 800 ℃ or form when higher, this carbon film is adamantine just as described above, has very strong cohesive force.In addition, this carbon film can make it become high-graphitized carbon film and has high strength by carbon film being heated to a high temperature that is lower than the stupalith fusing point.
It is 5 millimeters that the available poly-third butylene resin on the market is coated to thickness, and length and width direction size respectively is 40 millimeters Al
2O
3(surface irregularity is 10 microns) is heated to 1200 ℃ by way identical among the embodiment 1 then on the surface of ceramic post sintering spare.The result has formed a layer thickness and has been about 0.5 micron, based on the vitrification carbon film of amorphous carbon.This carbon film is when room temperature, and its specific resistance is about 2 * 10
-2Ω .cm, and also be adamantine and have a strong cohesive force with the same among the embodiment.
Embodiment 3
Fig. 2 represents the graph of a relation of Heating temperature and bonding part transverse strength.The available poly-third butylene resin on the market is coated to (this sintered part contains the BeO of 2% weight on the SiC ceramic post sintering spare of an electrical isolation, its lengthwise dimension respectively is 20 millimeters, its thickness is 30 millimeters), the heating resin bonds two sintered parts in argon atmospher then, intensity when in this case, being 40 millimeters by the mensuration distance between two points is carried out deflection test.Fig. 2 is given in bonding surface and applies 10 kilograms/millimeter
2Transverse strength during pressure and do not have transverse strength under the pressure condition.In both cases, when Heating temperature reached more than 1200 ℃, transverse strength all reached a maximum value.In the test specimen of pressurization, those are higher than 1200 ℃ of situations in temperature and carry out the agglutinating test specimen, and its fracture place is not at adhesive surface and at elsewhere.Formed carbon film thickness is approximately 1 micron, and the surfaceness of pottery is approximately 1 micron.
Under the situation that needs to exert pressure between when bonding adhesive surface, be preferably in Heating temperature and reach 400 ℃ or begin to exert pressure when higher again.The reason of doing like this is, all gases is separated out from organic compound when temperature is lower than 400 ℃, so will stay the undesirable defective such as pore etc. from the teeth outwards when gas is stayed these surfaces.
As mentioned above, according to the present invention, by all applying the carbon containing organic compound on the face of stupalith adhesive surface or on two faces, this organic compound of heating makes it decompose this method to form carbon film, just a pottery can be bonded together securely with another pottery by this layer carbon film in inert atmosphere then.This point is confirmed.
Ultimate analysis is carried out in the bonding part, and the result shows at adhesive surface not to be had to find because the peak value that carbon causes.The result should be such, because the carbon that thermolysis produces infilters in the stupalith by diffusion.Even the composite members that heating has prepared in air, two portions are not peeled off mutually yet, and its intensity is basic with the same before the heating.
Embodiment 4
At Si
3N
4Apply available liquid bisphenol A type Resins, epoxy on the market on the surface of ceramic post sintering spare equably, the diameter of this sintered part is 30 millimeters, and length is 100 millimeters, and its surfaceness is 10 microns, and the epoxy equivalent (weight) of above-mentioned Resins, epoxy is 186, and molecular weight is 330.Heat resin by mode identical among the embodiment 1 then in argon atmospher, the result forms the hard carbon film that a layer thickness is approximately 1 micron, and carbon film is bonded in Si securely
3N
4On the surface of ceramic post sintering spare.This layer carbon film mainly adds a spot of crystallization graphite again by amorphous carbon and formed.Fig. 3 is the auger analysis result of the carbon film that obtained.Can see that from rational curve shown in Figure 3 carbon (c) is considered to be diffused into Si
3N
4Remove and in sintered part, form one deck adhesive film in the sintered part.
Frictional coefficient to formed carbon film is measured, and finds that it is worth same Si
3N
4Comparing of ceramic post sintering spare is very little.Wearing test result shows, the wear resistance that has a sintered part of carbon film is approximately three times of sintered part of no carbon film.
The carbon film of present embodiment is to having good corrosion resistance such as chemical substances such as sodium hydroxide, phosphoric acid, the vitriol oil, concentrated hydrochloric acid, concentrated nitric acids, and therefore the protective membrane as ceramic briquetting is very effective.
Embodiment 5
Adopt method of the present invention, can (BeO that contains 2% weight be 10 than resistance with the SiC ceramic post sintering briquetting of electrical isolation
13Ω cm) with another piece Si
3N
4The ceramic post sintering briquetting bonds together.These two sintered compact, its length and width direction size all is 10 millimeters separately, length is 50 millimeters, treats that the maxxaedium roughness is 10 microns.This two block of material treat apply available bisphenol-type epoxy resin on the market (its epoxy equivalent (weight) is 190, and molecular weight is 380) on the bonding surface, in argon atmospher, press among the embodiment 1 same way as heating resin then.Two sintered compact are separated before temperature reaches 400 ℃, and at this moment the Resins, epoxy bubbing afterwards, applies 10 kilograms/millimeter to two agglomerate adhesive surfaces
2Pressure and by rate of heating identical among the embodiment 1 Resins, epoxy is heated to 1300 ℃, two block of material were bonded together in 1 minute in this temperature insulation.
To adopting three kinds of ceramic composites that this law obtained to carry out pliability test, the intensity of these three kinds of materials all reaches 25 kilograms/millimeter as a result
2Or it is higher.Fracture does not occur in the bonding part but other positions in these three kinds of materials.
Embodiment 6
Adopting two kinds of diameters is 10 millimeters, and length is 100 millimeters stupalith.The available alkyd resin on coating one deck market for the treatment of on the bonding surface at one of two materials is heated to 1500 ℃ by same way as among the embodiment 1 with resin in argon atmospher, allow its naturally cooling then.Reached before 350 ℃ in temperature, treat that the agglutinating material separates, after the alkyd resin bubbing, treat to apply on the bonding surface 5 kilograms/millimeter at two materials
2Pressure.The intensity of the ceramic composite that obtains like this reaches 30 kilograms/millimeter
2(room temperature), its fracture place are not at adhesive surface and at other position.
Embodiment 7
At S
I3N
4, S
iC and A
L2O
3Coating bisphenol A type epoxy resin (epoxy equivalent (weight) 183 is gone up on each surface of three kinds of ceramic post sintering briquettings, molecular weight 330), in argon atmospher, heat this resin to 800 ℃ so that on the surface of each sintered compact, form the hard vitrification carbon film of one deck then by same way as among the embodiment 1.Then, listed each braze material in the table 1 is added on the described surface, so just can carries out the wetting property test of braze material.S
iThe C sintered compact is with identical among the embodiment 5.List the result who various braze materials is carried out the wetting property test in the table 1.
The composition of listed each braze material is recently represented with weight percent in the table 1.In the wetting property test, heating is carried out in argon atmospher, and the temperature during the wetting property test is represented with bracket in table 1.Each ceramic surfaceness is about 1 micron.And it is identical among SC sintered compact and the embodiment 5.
Table 1
◎: the good wetted area of wetting property is 5 times of former braze material
O: the good wetted area of wetting property is about 2 times of former braze material
△: wetting property difference wetted area is identical with former braze material basically
In all cases, when carbon film of the present invention does not form on ceramic surface, then the pottery of being measured is (the seeing Table the mark △ in 1) of being on duty mutually with the wetting property of braze material combination.But just as shown in table 1, according to this invention at present, pottery can improve greatly with the wetting property of braze material.
For S
I3N
4Pottery is when braze material contains C
rThe time, wetting property good especially (seeing mark ◎) then.
To S
I3N
4Pottery and N
i-19C
rThe result that the composition of bonding surface is analyzed between-the 11P shows, can observe at the adhesive surface place because C
rThe peak value that causes.Have reason thus to think, for S
I3N
4Pottery has the carbide lamella of chromium to form at the adhesive surface place.
In other words, can think that the carbon film on the ceramic surface has impelled S
I3N
4In S
iSame C
rThereby react and generate the transition layer of the silicide of chromium at the adhesive surface place, the peak value that does not have discovery to cause at the adhesive surface place after the bonding by carbon.Can also think that in the bonding process carbon is diffused in the metal or in the pottery.Therefore, even heating does not have the oxidative phenomena appearance of carbon with the Ceramic Composite goods that method of the present invention obtained in air yet, do not have retroaction and produce.
When braze material contains manganese, S
iC pottery and Al
2O
3Both wetting properties all fine (seeing mark ◎) of pottery.Can think thus, for S
iC or Al
2O
3, the carbon film on the ceramic surface impels S
iS in the C pottery
iPerhaps Al
2O
3The S that is contained in the pottery
iO
2With manganese in the braze material responding layer of the silicide that generates manganese that reacts, thereby produce a strong adhesive surface.
Embodiment 8
-S
I3N
4(epoxy equivalent (weight) is 290 to the bisphenol A type epoxy resin that can buy on the coating market on the surface of ceramic post sintering briquetting, molecular weight is 710), the thickness of this briquetting is 5 millimeters, length and width direction size respectively is 30 millimeters, surfaceness is 5 microns, resin is heated to 1000 ℃ of top temperatures, is incubated 1 minute, allow its naturally cooling then.
By such method, at S
I3N
4Form a layer thickness on the surface of ceramic post sintering briquetting and be about 1 micron vitrification carbon film.Then, at S
I3N
4Add on the carbon film surface of ceramic post sintering briquetting and spread N
iSolder powder, its composition meets Nippon Standard JISBN
i-7 (is N
i19%(weight), Cr11%(weight) and the alloy of P), thickness be set again be 50 microns nickel foil thereon, synthetic integral body is heated to 1050 ℃ in argon atmospher, i.e. the fusing point of braze material allows its naturally cooling then.Soaking time in the time of 1050 ℃ is 1 minute, also loads 300 grams on the whole to prevent nickel foil slippage in the bonding process at synthetic in addition.
To by S
I3N
4Ceramic post sintering briquetting and nickel foil are formed, and three blocks of matrix materials that obtain by this law carry out spalling test, and the antistripping intensity that found that all three blocks of matrix materials is 20 kilograms/millimeter
2Or it is higher.
Embodiment 9
Adopt method identical among the embodiment at Al
2O
3Form one deck carbon film on the ceramic post sintering briquetting, the thickness of this briquetting is 2 millimeters, and length and width direction size respectively is 20 millimeters, and surfaceness is 5 microns.With thickness is 50 microns, contains Cu and 38%(weight) the Alloy Foil of Mn be placed on Al
2O
3On the surface of the lip-deep carbon film of ceramic post sintering briquetting, and then to place thickness thereon be 100 microns Copper Foil.This synthetic integral body is heated to 900 ℃ (this temperature is higher slightly than the fusing point of solder paper tinsel) in argon atmospher, and is incubated 1 minute.
To by Al
2O
3Ceramic post sintering briquetting and Copper Foil are formed, and five blocks of matrix materials that obtain by this law carry out spalling test, found that the antistripping intensity of all these five blocks of matrix materials all reaches 20 kilograms/millimeter
2Or higher, and rupture from Copper Foil.
At S
I3N
4Bisphenol A type epoxy resin (the epoxy equivalent (weight) 186 of the commercial supply of coating on the surface of ceramic post sintering briquetting, molecular weight 330), the thickness of this briquetting is 1 millimeter, the size of length direction and width respectively is 50 millimeters, surfaceness is 10 microns, with this resin by with embodiment 1 in same way as in argon atmospher, be heated to 1200 ℃ of top temperatures, be incubated 1 minute.
Can form the hard carbon film that a layer thickness is about 1 micron by such method.Then, add the method for thermogenesis Evaporation, at first make C by electron beam
rEvaporation also is deposited on Si
3N
4On the carbon film surface of ceramic post sintering briquetting, thereby formation thickness is 5 microns settled layer, then makes the Ni evaporation and is deposited on C
rSettled layer on, the thickness of this settled layer is about 5 microns.The carbon film of handling so further is heated to 1200 ℃ in a vacuum again, is incubated 10 minutes, allow its naturally cooling then, like this, Si
3N
4The surface just has been metallized.Is that 50 microns Copper Foil is bonded in the Si that has metallized with silver solder with thickness
3N
4On the surface.The result of adhesive surface spalling test shows that antistripping intensity reaches 30 kilograms/millimeter
2Or higher, peel off in all cases and all take place from silver-alloy brazing.
Embodiment 11
According to the inventive method, be that 15 millimeters and length are 20 centimetres Si with diameter
3N
4Ceramic post sintering briquetting homophase bonds together with the graphite of shape.The available bisphenol A type epoxy resin (epoxy equivalent (weight) 183 on the market for the treatment of on the bonding surface in the coating respectively at above-mentioned two materials, molecular weight 330), in argon atmospher by with embodiment 1 in identical mode this resin is heated to 400 ℃, then under this temperature insulation so that allow the abundant bubbing of resin.After this, treating to apply between the bonding surface 5 kilograms/millimeter
2Pressure, the rate of heating with 300 ℃ of per minutes is heated to 1500 ℃ with this resin again, with its naturally cooling of relief.
To measuring with the bending strength of the composite ceramic articles that this method obtained, the result shows that its bending strength is about 5 kilograms/millimeter
2, all goods all are in the graphite part fracture rather than in the bonding part.
Embodiment 12
Length and width direction size respectively is 10 millimeters, and length is 30 millimeters electrical isolation SiC ceramic post sintering briquetting (with among the embodiment 3 identical) and identical shaped graphite, both by with embodiment 3 in the identical mode method by pressurization bond together.To carrying out anti-reflecting bending strength determining by the composite ceramic articles that this method obtained, the result shows that its bending strength is 4 kilograms/millimeter
2Or higher, all goods all rupture in graphite part, rather than in the bonding part.
Embodiment 13
To contain 19%(weight) Cr and 11%(weight) P, particle mean size is that 30 microns the same liquid-state epoxy resin of nickelalloy solder powder (with employed identical among the embodiment 1) mixes mutually, the liquid resin dosage is that per 10 gram powder add 1 milliliter liquid.
The mixture that obtains at last is coated to Si
3N
4Make it be incubated 5 to 10 minutes down on the surface of sintered compact and in argon atmospher at 400 °～450 ℃.With mixture heating up to 1000 ℃, be incubated 1 minute then.The result is at Si
3N
4Form the nickelalloy solder layer that one deck has uniform thickness on the carbon film surface of sintered compact.That form prior to the fusing of solder owing to carbon film on ceramic surface and carbon film itself is very poor with the wetting property of solder powder, has not formed so there is the solder layer of carbon film like this.
Embodiment 14
Copper alloy powder and the liquid epoxies (with among the embodiment 1 identical) that with particle mean size are 30 microns mix mutually, this resin dosage is that 10 gram powder add 1 milliliters of liquid resin, with the mixture that obtains at last be coated in embodiment 3 on the surface of employed identical electrical isolation SiC sintered compact.Then with mixture 400 ° under 450 ℃, insulation is 5 to 10 minutes in argon atmospher, and then is heated to 900 ℃, is incubated 1 minute.The result forms the copper alloy solder layer that one deck has uniform thickness on the lip-deep carbon film of SiC sintered compact.
Embodiment 15
According to embodiment 13 in same way as, will be coated in Si with the employed identical Resins, epoxy among the embodiment 13 and the mixture of nickel solder powder
3N
4On the surface of sintered compact and under 400 °～450 ℃, insulation is 5 to 10 minutes in argon atmospher.Then with mixture heating up to 1000 ℃, be incubated 1 minute and kept in touch, as a result Si with the SUS304 steel (Nippon Standard) of market sale
3N
4Sintered compact and SUS304 steel bond together securely.
Embodiment 16
Ceramic blade (1) with shape shown in Fig. 4 is produced with a sintered compact, and this sintered compact is by containing 2%(weight) magnesium oxide and 2%(weight) the silicon nitride of beryllium oxide form.Metal blade (2) with shape shown in Fig. 4 is produced with the SCM steel alloy of JIS standard.Automobile turbocharger with shape shown in Fig. 4 is according to method of the present invention that ceramic blade and metal blade is bonding and produced.According to embodiment 1 in identical mode epoxy coating is treated adhesive segment to the axle (1) of ceramic blade (1), be heated to 1500 ℃ then so that form the vitrification carbon film (3) that a layer thickness is about 1 micron.
Subsequently, will be by 71%(weight) Ni, 19%(weight) Cr and 10%(weight) paste of the soldering alloyed metal powder formed of Si is packed between the axle (2) of above-mentioned carbon film and metal blade (2) and is heated to 1200 ℃ in argon atmospher, and the result confirms that ceramic blade bonds together by solder (4) securely with metal blade.
Embodiment 17
One turbo-supercharger makes as ceramic blade (1) with a sintered compact, the metal blade of this supercharging blower (2) adopt with embodiment 16 in identical mode carry out soldering, and sintered compact is by containing 2%(weight) the silicon carbide of beryllium oxide form.In this example, use 60%(weight) Mn, all the other alloys of forming for nickel are as braze material.Brazing temperature is 1050 ℃, and heating is carried out in argon atmospher.Ceramic blade and metal blade according to the turbo-supercharger that the inventive method obtained can bond together securely.
Describe in detail above the erect image like that, the present invention can obtain bonding by stupalith and ceramic composite that form, also can obtain bonding by stupalith and metallic substance and ceramic composite that form, and they all have very high bonding soundness.
Claims (17)
1, a kind of combined ceramic products is characterized in that it is to be bonded together by the hard carbon film of one deck by ceramic component and ceramic component or ceramic component and hardware to constitute, and talks about above-mentioned carbon film if desired and can include the metallic particles that forms on above-mentioned ceramic member bonding surface.
2, it is characterized in that according to desired combined ceramic products in the claim 1 described hard carbon film appears on the bonding surface of described ceramic component at least.
3, it is characterized in that according to desired combined ceramic products in the claim 1 carbon is to be diffused in the bonding surface of described ceramic component to go.
4, a kind of combined ceramic products is made up of the ceramic component that utilizes metal to bond together by hard carbon film, and each carbon film all is to form on the surface of described ceramic component.
5, it is characterized in that according to desired combined ceramic products in the claim 1 specific resistance of described carbon film when the room temperature is 10 Ω cm or smaller slightly.
6, it is characterized in that according to desired combined ceramic products in the claim 1 described metal is a kind of solder.
7, it is characterized in that according to the combined ceramic products that requires in the claim 1 described metal is a kind of solder between the metallic membrane that forms on the described carbon film.
8, it is characterized in that according to desired combined ceramic products in the claim 6 described metallic membrane and carbon react, with the surface of the bonding described metallic membrane of described carbon film on form a kind of carbide.
9, it is characterized in that according to desired combined ceramic products in the claim 1 specific resistance of described carbon film when the room temperature is 10 Ω cm.
10, it is characterized in that according to desired combined ceramic products in the claim 1 described metal is a kind of solder.
11, a kind of method of making combined ceramic products, combined ceramic products is made up of the ceramic component that bonds together or the ceramic component that bonds together and hardware, it is characterized in that described ceramic component being contacted with hardware with ceramic component or ceramic component by a kind of organic substance, organic substance can treat to contain on the bonding surface metallic particles at least one of described ceramic component and ceramic component or ceramic component and hardware if desired, described organic substance at high temperature decomposes and generates the hard carbon film of one deck, described organic substance is heated to its decomposition temperature or higher then in oxygen-free atmosphere.
12, it is characterized in that according to desired manufacture method in the claim 11 described organic substance is following class one of in all kinds of at least: Resins, epoxy, the poly-third butylene resin, alkyd resin, polyamide resin, polyvinyl chloride (PVC) RESINS, polyacrylonitrile, polyvinyl alcohol.
13, it is characterized in that according to desired manufacture method in the claim 11 Heating temperature is 800 ℃ or higher.
14, it is characterized in that applying on the described ceramic component pressure according to desired manufacture method in the claim 11.
15, it is characterized in that according to desired manufacture method in the claim 11 specific resistance of described carbon film when the room temperature is 10 Ω cm or smaller slightly.
16, it is characterized in that according to desired manufacture method in the claim 11 described metal is the Ni-Cr solder, Cu-Mn solder, Ag solder alloy or Fe solder alloy.
17, it is characterized in that according to desired manufacture method in the claim 11 described metal-powder is a kind of metal or solder alloy that can form carbide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101472.0A CN1005110B (en) | 1984-01-13 | 1985-04-01 | Combined ceramic products and its fabricating method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP346284A JPS60151292A (en) | 1984-01-13 | 1984-01-13 | Metallization of non-oxide ceramic |
| CN85101472.0A CN1005110B (en) | 1984-01-13 | 1985-04-01 | Combined ceramic products and its fabricating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101472A true CN85101472A (en) | 1987-01-10 |
| CN1005110B CN1005110B (en) | 1989-09-06 |
Family
ID=25741430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101472.0A Expired CN1005110B (en) | 1984-01-13 | 1985-04-01 | Combined ceramic products and its fabricating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1005110B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108031939A (en) * | 2017-11-10 | 2018-05-15 | 武汉凌云光电科技有限责任公司 | A kind of method of laser welding magnetic material |
| CN109665847A (en) * | 2019-03-06 | 2019-04-23 | 东北大学 | A kind of complete fine and close boron carbide ceramic composite and preparation method |
| CN114105644A (en) * | 2021-11-30 | 2022-03-01 | 咸阳师范学院 | High-wear-resistance ceramic material and preparation method and application thereof |
-
1985
- 1985-04-01 CN CN85101472.0A patent/CN1005110B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108031939A (en) * | 2017-11-10 | 2018-05-15 | 武汉凌云光电科技有限责任公司 | A kind of method of laser welding magnetic material |
| CN108031939B (en) * | 2017-11-10 | 2020-10-27 | 武汉凌云光电科技有限责任公司 | Method for laser welding of magnetic material |
| CN109665847A (en) * | 2019-03-06 | 2019-04-23 | 东北大学 | A kind of complete fine and close boron carbide ceramic composite and preparation method |
| CN109665847B (en) * | 2019-03-06 | 2021-05-28 | 东北大学 | Fully-compact boron carbide ceramic composite material and preparation method thereof |
| CN114105644A (en) * | 2021-11-30 | 2022-03-01 | 咸阳师范学院 | High-wear-resistance ceramic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1005110B (en) | 1989-09-06 |
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